JP2005015496A - Metallic soap containing molybdenum soap and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-quality homogeneous multicomponent metallic soap containing molybdenum soap in a high yield. <P>SOLUTION: The metallic soap containing molybdenum soap is produced by reacting a fatty acid with a molybdenum compound in the presence of a fatty acid and a metal compound that form a metallic soap having ≤120°C softening point. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is applied to an adhesive for promoting the adhesion between a steel cord for radial tire and rubber, a curing agent for unsaturated polyester resin, a curing accelerator for paint, a lubricant, a petroleum additive, a catalyst for various chemical reactions, and the like. The present invention relates to a molybdenum soap-containing composite metal soap and a method for producing the same.

Metal soaps mainly composed of cobalt and nickel are produced by, for example, a metathesis method in which a sodium naphthenate aqueous solution and a metal sulfate aqueous solution are reacted, or a direct method in which naphthenic acid and a metal salt are directly reacted.
However, when synthesizing metal soaps with molybdenum as the central metal, such as molybdenum naphthenate, the reactivity of fatty acid with metal salts such as molybdenum trioxide, ammonium molybdate, and sodium molybdate, which are the raw materials for molybdenum, is low. In addition, it is difficult to synthesize fatty acid molybdenum soap with high yield, and the following methods have been proposed.

A method of reacting a molybdenum compound with a monocarboxylic anhydride (Patent Document 1 (Japanese Patent Laid-Open No. 6-219990))
A method of using acetic anhydride to obtain molybdenum monocarboxylate by reacting a molybdenum compound with monocarboxylic acid (Patent Document 2 (JP-A-6-48978))
A method in which molybdic acid produced by the precipitation method is washed with water without drying and then reacted with monocarboxylic acid by heating (Patent Document 3 (Japanese Patent Publication No. 63-35616))
A method of reacting an alkali metal salt of molybdic acid, molybdenum halide, ammonium molybdate, molybdenum oxide and ammonia or a mixture thereof with a monocarboxylic acid at 100 to 300 ° C. (Patent Document 4 (Japanese Patent Publication No. 52-50768))
・ Production of organomolybdenum compounds in a final state in which the above alcohols are not present by heating and reacting molybdates reacted with hydrochloric acid in aliphatic alcohols with organic acids such as higher fatty acids, naphthenic acids, or resin acids. Method (Patent Document 5 (Japanese Patent Publication No. 46-2497))
-Method of heating molybdenum trioxide, oxalic acid, water, hexanoic acid in the reaction of molybdenum and carboxylic acid (Patent Document 6 (Japanese Patent Publication No. 42-21326))
Etc.
JP-A-6-219990 JP-A-6-48978 JP-B 63-35616 Japanese Patent Publication No.52-50768 Shoko 46-2497 Japanese Patent Publication No.42-21326

However, molybdenum soaps obtained by these synthesis methods contain unreacted fatty acids. This is because the reactivity between molybdenum and fatty acid is low and the softening point of molybdenum soap is high, and it solidifies as the reaction proceeds. Unreacted fatty acid is a metal containing molybdenum soap. The presence of the soap is often unfavorable because it often reduces the properties of the soap.
Moreover, when preparing the composite metal soap comprised with molybdenum soap and another metal soap, the metal soap synthesize | combined by another batch will be mixed with a molybdenum soap. At this time, the fatty acid contained in the molybdenum soap is preferable from the viewpoint of mixing, but the presence of the fatty acid has caused the deterioration of the characteristics of the composite metal soap, as in the case of producing the molybdenum soap alone. On the other hand, when the amount of unreacted fatty acid in the molybdenum soap is reduced, it becomes difficult to prepare a uniform composite metal soap because the liquid becomes solidified or has a high viscosity.

  In this way, the above method is insufficient from the viewpoint of producing a composite soap composed of a mixture of molybdenum soap and other metal soaps in good yield, leaving uniform and unreacted fatty acids, At present, no method has been found for economically producing molybdenum soap-containing metal soap with low by-products and good storage stability.

  Under such circumstances, an object of the present invention is to produce a uniform molybdenum soap-containing composite metal soap with a high yield.

  As a result of studying the development of a method for producing a uniform molybdenum soap-containing composite metal soap with high yield, the present inventors have found that in the presence of a fatty acid and a metal compound that form a metal soap having a softening point of 120 ° C. or lower. Alternatively, by synthesizing molybdenum soap by the reaction of a fatty acid and a molybdenum compound in the presence of a metal soap having a softening point of 120 ° C. or lower, it was found that a uniform molybdenum-containing composite metal soap can be easily produced in a high yield, leading to the present invention. .

  That is, the present invention provides (1) uniform molybdenum characterized by reacting a molybdenum compound and a fatty acid in the presence of a fatty acid and a metal compound that form a metal soap having a softening point of 120 ° C. or less without adding oxalic acid. Method for producing soap-containing composite metal soap, (2) Uniform molybdenum soap-containing composite metal, characterized in that molybdenum soap is synthesized in the presence of metal soap having a softening point of 120 ° C. or less without adding oxalic acid. (3) The uniform ratio according to (1) or (2) above, wherein the element ratio of molybdenum and metal other than molybdenum contained in the molybdenum soap-containing metal soap is 1/2 or less. (4) A metal soap other than molybdenum soap having a softening point of 120 ° C. or lower. A homogeneous molybdenum soap-containing composite metallic soap that relates.

  According to the present invention, a uniform molybdenum soap-containing composite metal soap can be produced with good yield. Molybdenum soap-containing metal soap produced according to the present invention includes an adhesive that promotes adhesion between a steel cord for radial tire and rubber, a curing agent for unsaturated polyester resin, a curing accelerator for paint, a lubricating oil, or a petroleum additive. It is useful as a catalyst for various chemical reactions.

  The metal soap having a softening point of 120 ° C. or lower used in the present invention includes magnesium, calcium, strontium, barium, zinc, cadmium, nickel, titanium, aluminum and other metal oxides, hydroxides, carbonates, alkoxides, and organic metals. Metal soaps synthesized from compounds and fatty acids can be used. Specifically, zinc naphthenate, zinc neodecanoate, nickel naphthenate, nickel neodecanoate, magnesium tall oilate, etc. can be exemplified, and naturally two or more kinds may be used in combination. Therefore, examples of the metal soap-forming fatty acid having a softening point of 120 ° C. include naphthenic acid, neodecanoic acid, tall oil acid and the like. In order to synthesize a highly reactive and uniform molybdenum-containing metal soap, it is preferable to use zinc soap, nickel soap or cobalt soap, depending on the expected properties.

When a metal soap having a softening point exceeding 120 ° C. is used, the viscosity becomes too high at the end of the reaction when synthesizing molybdenum soap, so that the reaction is difficult to complete. The softening point of the metallic soap in which molybdenum soap coexists in the synthesis is preferably as low as possible in terms of the progress of the reaction, but it also affects the softening point of the molybdenum metallic soap. More preferably, it is 30 ° C. or higher.
In the present invention, it is preferable that the element ratio of molybdenum and metal other than molybdenum contained in the molybdenum soap-containing metal soap is ½ or less. When the ratio exceeds 1/2, the softening point and viscosity of the molybdenum soap are not sufficiently lowered and it is difficult to proceed the reaction.

  The fatty acid used in the present invention is a natural or synthetic saturated or unsaturated fatty acid having a main chain of 6 to 30 carbon atoms or a mixture thereof. Specifically, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxy Examples thereof include stearic acid, dimer acid, tall oil acid, naphthenic acid, neodecanoic acid, resin acid, and natural fat and oil fatty acids such as fish oil hardened fatty acid and beef tallow hardened fatty acid.

As the molybdenum compound used in the present invention, molybdenum oxide, molybdenum ammonium salt, sodium salt, molybdenum acetylacetonate and the like can be used.
Examples of the molybdenum soap include soaps formed from the above-described fatty acid and molybdenum, and specific examples include molybdenum naphthenate, molybdenum neodecanoate, and resin acid molybdenum.

Examples of the molybdenum soap-containing composite metal soap that can be produced according to the present invention include the following compounds.
Examples of metal soaps composed of two kinds of metals include Zn naphthenate / Mo naphthenate, Ni naphthenate / Mo naphthenate, Co naphthenate / Mo naphthenate, Zn neodecanoate / Mo naphthenate, Ni / decano decanoate. Acid Mo, neodecanoic acid Co / naphthenic acid M. , Zn neodecanoate / Mo neodecanoate, (Neodecanoic acid-naphthenic acid) (Zn / Mo), (Neodecanoic acid-resin acid) (Zn / Mo), (Resin acid-naphthenic acid) (Zn / Mo), (Neodecane) Acid-naphthenic acid) Zn / Mo naphthenic acid, (tall oil acid-naphthenic acid) Zn / naphthenic acid Mo, (stearic acid-naphthenic acid) Zn / naphthenic acid Mo, (neodecanoic acid-naphthenic acid) Zn / neodecanoic acid Mo , (Neodecanoic acid-resin acid) Zn / resin acid Mo, (naphthenic acid-resin acid) Zn / resin acid Mo, naphthenic acid Ni / naphthenic acid Mo, neodecanoic acid Ni / neodecanoic acid Mo, stearic acid Ni / stearic acid Mo , (Neodecanoic acid-naphthenic acid) (Ni / Mo), (Neodecanoic acid-resin acid) (Ni / Mo), (Resin acid-naphthenic acid) (Ni / Mo) (Neodecanoic acid-naphthenic acid) Ni / Mo naphthenic acid, (Tall oil acid-Naphthenic acid) Ni / Naphthenic acid Mo, (Stearic acid-naphthenic acid) Ni / Naphthenic acid Mo, (Neodecanoic acid-naphthenic acid) Ni / Neodecane Acid Mo, (neodecanoic acid-resin acid) Ni / resin acid Mo, (naphthenic acid-resin acid) Ni / resin acid Mo, naphthenic acid Co / naphthenic acid Mo, neodecanoic acid Co / neodecanoic acid Mo, stearic acid Co / stearin Acid Mo, (Neodecanoic acid-naphthenic acid) (Co / Mo), (Neodecanoic acid-resin acid) (Co / Mo), (Resin acid-naphthenic acid) (Co / Mo), (Neodecanoic acid-naphthenic acid Co / Naphthenic acid Mo, (Tall oil acid-Naphthenic acid) Co / Naphthenic acid Mo, (Stearic acid-Naphthenic acid) Co / Naphthenic acid Mo, (Neodeca Acid mononaphthenic acid) Co / neodecanoic acid Mo, (neodecanoic acid-resin acid) Co / resin acid Mo, (naphthenic acid-resin acid) Co / resin acid Mo, naphthenic acid Ti / naphthenic acid Mo, neodecanoic acid Ti / neodecane Acid Mo, (Neodecanoic acid-naphthenic acid) (Ti / Mo), (Neodecanoic acid-naphthenic acid) Co / Neodecanoic acid Mo.

Moreover, as a metal soap which consists of 3 or more types of metals, for example, naphthenic acid (Zn—Ni) / naphthenic acid Mo, neodecanoic acid (Zn—Ni) / neodecanoic acid Mo, stearic acid (Zn—Ni) stearic acid Mo, (Neodecanoic acid-Naphthenic acid)
(Zn—Ni) / Naphthenic acid Mo, (Tall oil acid-naphthenic acid) (Zn—Ni)
/ Naphthenic acid Mo, (Stearic acid-Naphthenic acid) (Zn-Ni) / Naphthenic acid Mo, (Neodecanoic acid-naphthenic acid) (Zn-Ni) / Neodecanoic acid Mo, (Neodecanoic acid-resin acid) (Zn-Ni ) / Resin acid Mo, (naphthenic acid-resin acid) (Zn-Ni) resin acid Mo, (neodecanoic acid-naphthenic acid) (Zn-Mg) / naphthenic acid Mo, naphthenic acid (Zn-Ni-Co) / naphthene Acid Mo, neodecanoic acid (Zn-Ni-Co) / neodecanoic acid Mo, stearic acid (Zn-Ni-Co) / stearic acid Mo, (neodecanoic acid-naphthenic acid) (Zn-Ni-Co) / Mo naphthenic acid, (Tall oil acid-naphthenic acid) (Zn-Ni-Co) / Naphthenic acid Mo, (Stearic acid-naphthenic acid) (Zn-Ni-Co) / Naphthenic acid Mo, (Neodecanoic acid-Na Tenenoic acid) (Zn-Ni-Co) / Neodecanoic acid Mo, (Neodecanoic acid-resin acid) (Zn-Ni-Co) / Resin acid Mo, (Naphthenic acid-resin acid) (Zn-Ni-Co) / Resin Acid Mo etc. can be illustrated.

  In the practice of the present invention, a metal compound having a softening point of 120 ° C. or less must coexist or a molybdenum compound and a fatty acid must be reacted while synthesizing the metal soap. In the reverse order, for example, when molybdenum soap is synthesized first, the viscosity increases as the reaction progresses, and in some cases solidifies so that the reaction does not end and the molybdenum soap-containing metal soap is produced uniformly or in good yield. I can't.

  In general, the reactivity of a molybdenum compound and a fatty acid is low, and even if a molybdenum compound and a metal compound other than molybdenum and a fatty acid are added at the same time to start the reaction, the reaction of the metal compound other than molybdenum proceeds first and the softening point is low. There is no problem because it produces soap. In some cases, a temperature program may be effective in which a metal soap having a low softening point is first generated at a temperature of 180 ° C. or lower, and the temperature is set to 200 ° C. or higher when molybdenum soap is synthesized. Further, after the reaction between the molybdenum compound and the fatty acid is allowed to proceed to some extent, metal soap having a low softening point may be added.

As a method for producing the molybdenum compound used in the present invention, methods reported so far can be used. For example, a method for producing molybdenum salts (US Pat. No. 3,362,972) comprising heating a metal oxalic acid compound of the group consisting of +6 valence molybdenum and a hydrocarbon carboxylic acid having 4 to 50 carbon atoms, a molybdenum compound A method of reacting directly at high temperature while removing water from the reaction mixture (US Pat. No. 3,578,690), a method of heating molybdenum trioxide, oxalic acid, water and hexanoic acid in the reaction of molybdenum and carboxylic acid (Japanese Patent Publication No. 42-21326). ), An aqueous molybdenum compound solution having a valence of IV is reduced in acidity, mixed with a high-boiling organic acid or alcohol, reacted by heating, and simultaneously distilled off water and easily volatile compounds. Use a method for producing a compound (Japanese Patent Publication No. 51-40059). Is possible.
However, when using a compound having strong oxidation or reduction ability such as a large amount of oxalic acid, it is better not to use it because there is a risk of decomposing the metal soap synthesized or prepared in the previous step.
When synthesizing molybdenum soap, water is generally used as disclosed in Japanese Examined Patent Publication No. 42-21326. However, it takes time to remove water, and there is a problem with the danger of heating to high temperature in the presence of water. There is. In the production method previously proposed (Japanese Patent Application No. 9-92335), the present inventors have a great influence on the yield of water in the reaction system, and the production is performed without adding water. It has been found that molybdenum soap can be manufactured extremely safely and with good yield. Therefore, in order to achieve the present invention, water may be added, but it is preferable not to add water because the above-mentioned problems are solved.

Oxalic acid may be used when synthesizing the molybdenum soap. However, in order to decompose the metal soap synthesized before the molybdenum soap, it is better to reduce the addition amount or not add it in the present invention. When the amount of oxalic acid used is large, the metal soap may decompose and the amount of solid substance residue after the reaction may increase.
The fatty acid used in the synthesis of molybdenum soap or metal soap having a softening point of 120 ° C. or lower may be one kind or a mixture of two or more kinds of fatty acids.

As a method for producing a metal soap having a softening point of 120 ° C. or lower, a method in which a metal compound and a fatty acid are directly reacted is preferable. In the reaction, an alcohol, an aromatic or paraffinic organic solvent may be used, but it is desirable to react without adding a solvent in order to advance the reaction efficiently.
Molybdenum soap alone has a high softening point, making it difficult to react with metal compounds or to mix with metal soaps other than molybdenum.

  According to the present invention, the metal component is uniform and the molybdenum soap-containing metal soap can be produced in a high yield because the metal soap having a low softening point is used as a reaction solvent, so that stirring is possible until the end of the reaction. It is thought that it was because of.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples. All syntheses were performed in a nitrogen atmosphere. The progress of the reaction was judged by the amount of toluene insoluble since the molybdenum compound and the metal compound were not dissolved in toluene.

(Example 1)
Synthesis example of (molybdenum / zinc) composite soap Neodecanoic acid 153.9 g (0.900 mol), ammonium molybdate ((NH ₄ ) ₈ Mo ₇ O ₂₄ 4H ₂ O) 12.2 g (0.010 mol, Mo0. 069 mol) and 33.8 g (0.415 mol) of zinc oxide were mixed in a 500 ml flask and heated and stirred for 10 hours while removing volatile components at an oil temperature of 240 ° C. Thereafter, it was dried under reduced pressure at an oil temperature of 160 ° C. and 20 mmHg for 2 hours to obtain 187.7 g of neodecanoic acid (Zn / Mo) (6/1) composite soap. The toluene insoluble content of the obtained Zn neodecanoate / Mo neodecanoate was <1% with respect to the obtained molybdenum soap-containing metal soap.

(Example 2)
When 20.3 g (0.016 mol, 0.115 mol) of ammonium molybdate and 28.6 g (0.115 mol) of naphthenic acid were placed in a 500 ml flask and reached 240 ° C., 237.3 g of neodecanoic acid (1. 388 mol) and 56.5 g (0.694 mol) of zinc oxide were added to another 500 ml flask, and zinc neodecanoate synthesized by heating and stirring at 160 ° C. for 40 minutes was added, and ammonium molybdate and naphthenic acid were further added at 240 ° C. For 10 hours. The toluene insoluble content of the obtained neodecanoate Zn / Mo naphthenate was <1% with respect to the obtained metal soap-containing metal soap.

(Comparative Example 1)
20.3 g of ammonium molybdate (0.016 mol, 0.115 mol of Mo) and 28.6 g of naphthenic acid (0.115 mol) were placed in a 500 ml flask and heated at 240 ° C. for 40 hours. It was synthesized in another 500 ml flask with 237.3 g (1.388 mol) of neodecanoic acid and 56.5 g (0.694 mol) of zinc oxide, and added with neodecanoic acid Zn synthesized by heating and stirring at 160 ° C. for 40 minutes. And heated and mixed at 180 ° C. for 2 hours. Mixing of naphthenic acid Mo and Zn neodecanoate was insufficient because the naphthenic acid Mo was solidified and could not be stirred, and the resulting metal soap was non-uniform. The toluene insoluble content of the obtained neodecanoate Zn / Mo naphthenate was 7.0% with respect to the obtained metal soap-containing metal soap.

(Comparative Example 2)
Neodecanoic acid (Zn / Mo) soap was synthesized in the same manner as in Example 1 except that the Mo / Zn molar ratio was set to 0.6. The toluene insoluble content of the obtained neodecanoic acid (Zn / Mo) was 5.0% with respect to the obtained molybdenum soap-containing metal soap.

(Reference Example 1)
Neodecanoic acid 150.0 g (0.877 mol), ammonium molybdate ((NH ₄ ) ₈ Mo ₇ O ₂₄ 4H ₂ O) 11.9 g (0.010 mol, Mo 0.067 mol), oxalic acid 4.3 g ( 0.034 mol) and 33.0 g (0.40 mol) of zinc oxide were mixed in a 500 ml flask and heated and stirred for 10 hours while removing volatile components at an oil temperature of 240 ° C. Thereafter, the mixture was dried under reduced pressure at an oil temperature of 160 ° C. and 20 mmHg for 2 hours to obtain neodecanoic acid (Zn / Mo) (6/1) composite soap. The toluene insoluble matter was 3.0%.

Claims (4)

Uniform molybdenum soap-containing composite metal soap, characterized by reacting a molybdenum compound and a fatty acid in the presence of a fatty acid and a metal compound that form a metal soap having a softening point of 120 ° C. or less without adding oxalic acid . A method for producing a uniform molybdenum soap-containing composite metal soap, characterized in that molybdenum soap is synthesized in the presence of a metal soap having a softening point of 120 ° C. or less without adding oxalic acid. 3. The method for producing a uniform composite metal soap containing molybdenum soap according to claim 1, wherein the element ratio of molybdenum to a metal other than molybdenum contained in the molybdenum soap-containing metal soap is ½ or less. Molybdenum soap-containing composite metal soap containing metal soap other than molybdenum soap having a softening point of 120 ° C. or lower.